JP2611289B2 - Method for producing polyamic acid or polyamic acid ester - Google Patents
Method for producing polyamic acid or polyamic acid esterInfo
- Publication number
- JP2611289B2 JP2611289B2 JP31920687A JP31920687A JP2611289B2 JP 2611289 B2 JP2611289 B2 JP 2611289B2 JP 31920687 A JP31920687 A JP 31920687A JP 31920687 A JP31920687 A JP 31920687A JP 2611289 B2 JP2611289 B2 JP 2611289B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- polyimide
- acid
- tetracarboxylic
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明はポリアミド酸又はポリアミド酸エステルの製
造法に関する。The present invention relates to a method for producing a polyamic acid or a polyamic acid ester.
(従来の技術) 従来、ポリイミドは一般にジアミンとテトラカルボン
酸二無水物を溶媒中で反応させてポリアミド酸を生成
し、これを脱水閉環するかまたはジイソシアネートとテ
トラカルボン酸二無水物を反応させて直接ポリイミドを
生成させる等の方法で得られている。(Prior art) Conventionally, polyimide generally produces a polyamic acid by reacting a diamine and a tetracarboxylic dianhydride in a solvent and subjecting this to dehydration ring closure or reaction of a diisocyanate with a tetracarboxylic dianhydride. It is obtained by a method such as directly producing polyimide.
こうして得られるポリアミド酸およびポリイミドの特
性は用いるジアミン、ジイソシアネート、テトラカルボ
ン酸二無水物等の選択と、これらの組合せで定まり、耐
熱性に優れるもの、可とう性に富むもの、溶解性に優れ
るもの等、種々知られている。The properties of the polyamic acid and polyimide obtained in this way are determined by the selection of the diamine, diisocyanate, tetracarboxylic dianhydride and the like to be used, and the combination thereof, and are excellent in heat resistance, flexible, and excellent in solubility. And so on.
その中で、テトラカルボン酸二無水物として芳香族テ
トラカルボン酸二無水物を用いたポリイミドは優れた耐
熱性及び機械特性を有しているが、ポリイミドを作製す
るための温度は300℃以上を必要とし、得られたポリイ
ミドの外観はかつ色に着色している。Among them, polyimides using aromatic tetracarboxylic dianhydrides as tetracarboxylic dianhydrides have excellent heat resistance and mechanical properties, but the temperature for producing polyimides is 300 ° C or higher. As needed, the appearance of the resulting polyimide is also colored.
一方、ポリイミドは種々の分野へ応用されるようにな
つてきており、例えば、液晶表示素子の配向膜などの光
デバイス分野にも用いられるようになつている。しかし
ながら、上記の芳香族テトラカルボン酸二無水物を用い
たポリイミドでは透明性が低いこと、及び液晶表示素子
自身の耐熱性が乏しいため、ポリイミド化の工程で素子
そのものが分解することから使用することが難かしい。
このため、低温でポリイミド化し、かつ得られたポリイ
ミドの透明性が良好であるテトラカルボン酸二無水物と
して、1,2,3,4−ブタンテトラカルボン酸二無水物など
の脂肪族テトラカルボン酸二無水物、あるいは1,2,4,5
−シクロヘキシルテトラカルボン酸二無水物、1,2,3,4
−シクロペンタンテトラカルボン酸二無水物などの脂環
式テトラカルボン酸二無水物などが知られている。On the other hand, polyimide has been applied to various fields, and for example, is also used in the field of optical devices such as an alignment film of a liquid crystal display element. However, since the polyimide using the above aromatic tetracarboxylic dianhydride has low transparency and the heat resistance of the liquid crystal display device itself is poor, the device itself is decomposed in the process of polyimide conversion, so that it should be used. Is difficult.
Therefore, as a tetracarboxylic dianhydride which is polyimide at a low temperature and the obtained polyimide has good transparency, aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic dianhydride Dianhydride or 1,2,4,5
-Cyclohexyltetracarboxylic dianhydride, 1,2,3,4
-Alicyclic tetracarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride are known.
(発明が解決しようとする問題点) 従来から知られている脂肪族テトラカルボン酸二無水
物を用いたポリイミドは耐熱性が非常に低下するという
欠点を有している。(Problems to be Solved by the Invention) A conventionally known polyimide using an aliphatic tetracarboxylic dianhydride has a drawback that heat resistance is extremely reduced.
また、脂環式テトラカルボン酸である1,2,4,5−シク
ロヘキシルテトラカルボン酸二無水物を用いたポリイミ
ドはガラス転移温度、熱分解開始温度は脂肪族テトラカ
ルボン酸二無水物に比較して高いが非常にもろいことが
確認された。あるいは1,2,3,4−シクロペンタンテトラ
カルボン酸二無水物はポリアミド酸の重合度が上がら
ず、やはり非常もろいポリイミドしか得られない。Polyimide using 1,2,4,5-cyclohexyltetracarboxylic dianhydride, which is an alicyclic tetracarboxylic acid, has a glass transition temperature and a thermal decomposition onset temperature which are lower than those of aliphatic tetracarboxylic dianhydride. High but very fragile. Alternatively, 1,2,3,4-cyclopentanetetracarboxylic dianhydride does not increase the degree of polymerization of polyamic acid, so that only a very fragile polyimide can be obtained.
本発明は、従来の問題を解決し低温でポリイミド化
し、良好な透明性、耐熱性及び機械特性を併せ持つポリ
イミドを提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide which solves the conventional problems and is made into a polyimide at a low temperature, and has good transparency, heat resistance and mechanical properties.
(問題点を解決するための手段) 本発明は、一般式〔IV〕 (式中、R3及びRは各々独立して、酸素原子、二個の水
酸基又は水酸基とメトキシ基若しくはエトキシ基を示
す)で表わされる化合物と 一般式〔V〕 H2N−R2−NH2 〔V〕 (式中、R2は二価の基を示す)で表わされるジアミンと
を反応させることを特徴とする下記一般式〔I〕、〔I
I〕又は〔III〕で表わされる構造単位からなるポリアミ
ド酸又はポリアミド酸エステルの製造法に関する。(Means for Solving the Problems) The present invention provides a compound represented by the general formula [IV]: (Wherein R 3 and R each independently represent an oxygen atom, two hydroxyl groups, or a hydroxyl group and a methoxy group or an ethoxy group) and a compound represented by the general formula [V] H 2 N—R 2 —NH 2 [V] (wherein R 2 represents a divalent group) characterized by reacting with a diamine represented by the following general formulas [I], [I]
The present invention relates to a method for producing a polyamic acid or a polyamic ester comprising a structural unit represented by I) or [III].
(上記〔I〕、〔II〕及び〔III〕の式中、R1は水素原
子、メチル基又はエチル基、R2は2価の基を示す) 以下、本発明について詳述する。 (In the above formulas [I], [II] and [III], R 1 represents a hydrogen atom, a methyl group or an ethyl group, and R 2 represents a divalent group.) Hereinafter, the present invention will be described in detail.
本発明の一般式〔I〕、〔II〕又は〔III〕で表され
る構造単位からなるポリアミド酸又はポリアミド酸エス
テルは、一般式〔IV〕で表わされる化合物と、一般式
〔V〕で表わされるジアミンを溶媒中で反応させて得ら
れる。一般式〔IV〕で表わされる化合物は、新規な化合
物であつて次式で示される様にビフエニル−3,4,3′,
4′−テトラカルボン酸テトラメチルエステルを水素化
反応させ、加水分解、脱水閉環及び/又はメタノール付
加で製造することができる。The polyamic acid or polyamic acid ester comprising a structural unit represented by the general formula (I), (II) or (III) of the present invention is a compound represented by the general formula (IV) and a compound represented by the general formula (V). Obtained in a solvent. The compound represented by the general formula [IV] is a novel compound and has a biphenyl-3,4,3 ',
It can be produced by subjecting 4'-tetracarboxylic acid tetramethyl ester to hydrogenation reaction, hydrolysis, dehydration ring closure and / or addition of methanol.
すなわち、ビフエニル−3,4,3′,4′−テトラカルボ
ン酸テトラメチルエステルをロジウム触媒存在下に水素
化反応させてジシクロヘキシル−3,4,3′,4′−テトラ
カルボン酸テトラメチルエステルとし、その後酸加水分
解あるいはアルカリ加水分解と酸析によつてジシクロヘ
キシル−3,4,3′,4′−テトラカルボン酸とする。その
後、必要に応じて加熱あるいは無水酢酸によつて脱水閉
環させてジシクロヘキシル−3,4,3′,4−テトラカルボ
ン酸二無水物とすることができる。さらにこのものにつ
いてアルコールを反応させジシクロヘキシル−3,4,3′,
4′−テトラカルボン酸ジエステルとすることができ
る。 That is, biphenyl-3,4,3 ', 4'-tetracarboxylic acid tetramethyl ester is hydrogenated in the presence of a rhodium catalyst to give dicyclohexyl-3,4,3', 4'-tetracarboxylic acid tetramethyl ester. After that, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid is obtained by acid hydrolysis or alkali hydrolysis and acid precipitation. Thereafter, if necessary, the ring may be dehydrated and closed with heating or with acetic anhydride to obtain dicyclohexyl-3,4,3 ', 4-tetracarboxylic dianhydride. Further reacting this with alcohol, dicyclohexyl-3,4,3 ',
It can be 4'-tetracarboxylic diester.
本発明の一般式〔I〕、〔II〕又は〔III〕で表わさ
れる構造単位からなるポリアミド酸又はポリアミド酸エ
ステルにおける一般式〔I〕、〔II〕及び〔III〕のR2
で示される二価の基は、一般式〔IV〕で示される化合物
と反応させる一般式〔V〕のジアミンのR2に対応する。
すなわちジアミンの種類によつて決まる。したがつて一
般式〔I〕、〔II〕又は〔III〕で表わされる構造単位
からなるポリアミド酸又はポリアミド酸エステルを経由
する一般式〔VI〕で表わされる構造単位からなるポリイ
ミドにおける一般式〔VI〕のR2で示される二価の基も一
般式〔V〕のジアミンのR2に対応する。すなわちジアミ
ンの種類によつて決まる。R 2 of the general formulas (I), (II) and (III) in the polyamic acid or polyamic acid ester comprising the structural unit represented by the general formula (I), (II) or (III) of the present invention
The divalent group represented by the formula corresponds to R 2 of the diamine of the general formula [V] to be reacted with the compound represented by the general formula [IV].
That is, it is determined by the type of diamine. Accordingly, the polyimide represented by the general formula [VI] comprising the structural unit represented by the general formula [VI] via a polyamic acid or a polyamic acid ester composed of the structural unit represented by the general formula [I], [II] or [III] divalent groups represented by R 2 in] also correspond to the R 2 diamines of the general formula (V). That is, it is determined by the type of diamine.
本発明に用いられる一般式〔V〕で表わされるジアミ
ンは、4,4′−ジアミノジフエニルエーテル、4,4′−ジ
アミノジフエニルメタン、4,4′−ジアミノフエニルス
ルホン、4,4′−ジアミノジフエニルサルファイド、ベ
ンジジン、メタフエニレンジアミン、パラフエニレンジ
アミン、2,2−ビス(4−アミノフエニル)プロパン、
ジアミノベンゾフエノン、1,5−ジアミノナフタレン、
2,6−ジアミノナフタレ、1,3−ビス(4−アミノフエノ
キシ)ベンゼン、1,4−ビス(4−アミノフエノキシ)
ベンゼン、4,4′−ジ(4−アミノフエノキシ)ジフエ
ニルスルホン、4,4′−ジ(3−アミノフエノキシ)ジ
フエニルスルホン、2,2−ビス(4−(4−アミノフエ
ノキシ)フエニル)プロパン、 である。The diamine represented by the general formula [V] used in the present invention is 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylsulfone, 4,4 ' -Diaminodiphenyl sulfide, benzidine, metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane,
Diaminobenzophenone, 1,5-diaminonaphthalene,
2,6-diaminonaphthale, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 4,4'-di (4-aminophenoxy) diphenylsulfone, 4,4'-di (3-aminophenoxy) diphenylsulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, It is.
R2で示される二価の基は、このようなジアミンから2
つのアミノ基を除いた残基である。The divalent group represented by R 2 is formed from such a diamine by 2
It is a residue excluding two amino groups.
本発明の新規なポリアミド酸又はポリアミド酸エステ
ル及びポリイミドを製造するに当つては、例えばN−メ
チル−2−ピロリドン、N,N−ジメチルアセドアミド、
N,N−ジメチルホルムアミド、ジメチルスルホキシド、
ヘキサメチルホスホルアミド、テトラメチレンスルホ
ン、p−クロルフエノール、p−ブロモフエノール、2
−クロル−4−ヒドロキシトルエン等の溶媒が用いられ
る。In producing the novel polyamic acid or polyamic ester and polyimide of the present invention, for example, N-methyl-2-pyrrolidone, N, N-dimethylacedamide,
N, N-dimethylformamide, dimethylsulfoxide,
Hexamethylphosphoramide, tetramethylene sulfone, p-chlorophenol, p-bromophenol, 2
A solvent such as chloro-4-hydroxytoluene is used.
本発明を実施するに当つては、一般式〔I〕、〔II〕
及び/又は〔III〕で表わされる構造単位からなるポリ
アミド酸の場合、好ましくはまず一般式〔V〕で表わさ
れるジアミンを上記不活性溶媒中に溶解した後、一般式
〔IV〕で表わされる化合物の1つであるジシクロヘキシ
ル−3,4,3′4′−テトラカルボン酸二無水物を加え、
好ましくは約80℃以下特に室温付近ないしそれ以下の温
度を保ちながら撹拌する。これによつて反応はすみやか
に進行し、かつ反応系の粘度は次第に上昇し、ポリアミ
ド酸が生成する。反応終了後、ポリアミド酸ワニスの粘
度を調整するために、反応に用いた溶媒の他に、ジエチ
レングリコールモノメチルエーテル、ジエチレングリコ
ールモノエチルエーテル、エチレングリコールモノブチ
ルエーテルなどのセロソルブ系溶媒を加えることができ
る。In carrying out the present invention, general formulas [I] and [II]
And / or in the case of a polyamic acid comprising a structural unit represented by [III], preferably, first, a diamine represented by the general formula [V] is dissolved in the above inert solvent, and then a compound represented by the general formula [IV] Dicyclohexyl-3,4,3'4'-tetracarboxylic dianhydride which is one of
Preferably, the mixture is stirred while maintaining the temperature at about 80 ° C. or lower, particularly around room temperature or lower. As a result, the reaction proceeds promptly, and the viscosity of the reaction system gradually increases to produce polyamic acid. After the completion of the reaction, in order to adjust the viscosity of the polyamic acid varnish, a cellosolve-based solvent such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and ethylene glycol monobutyl ether can be added in addition to the solvent used for the reaction.
一般式〔I〕、〔II〕又は〔III〕で表わされる構造
単位からなるポリアミド酸エステルを得るには、上記の
方法によつて合成したポリアミド酸のカルボン酸基をチ
オニルクロライド等を用いて酸クロライドとした後、メ
タノール、エタノール等のアルコールと反応させる方法
またはジシクロヘキシル−3,4,3′,4′−テトラカルボ
ン酸等を上記同様酸クロライドを経由してエステル化し
たもの、もしくはジシクロヘキシル−3,4,3′,4′−テ
トラカルボン酸二無水物等をアルコールで開環してジエ
ステル化したものを溶媒中でジアミン化合物と反応させ
る方法等によつて得られる。In order to obtain a polyamic acid ester comprising a structural unit represented by the general formula [I], [II] or [III], the carboxylic acid group of the polyamic acid synthesized by the above method is converted to an acid by using thionyl chloride or the like. Chloride and then reacting with an alcohol such as methanol or ethanol, or dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid or the like esterified via acid chloride as described above, or dicyclohexyl-3 , 4,3 ', 4'-Tetracarboxylic dianhydride and the like are obtained by a method in which ring-opening and diesterification with an alcohol are reacted with a diamine compound in a solvent.
一般式〔I〕、〔II〕及び〔III〕中のR1が一価の炭
化水素基のときR1は上記のポリアミド酸エステルを得る
ときに使用されるアルコールに対応する。すなわちアル
コールからヒドロキシル基を除いた部分がR1である。こ
のポリアミド酸またはポリアミド酸エステルをポリイミ
ドに転化せしめるには、100〜300℃の温度で好ましくは
30分〜50分間熱処理する。こうすることによりポリアミ
ド酸の場合、脱水、閉環し、ポリアミド酸エステルの場
合、脱アルコール、閉環し一般式〔VI〕で表わされる構
造単位を含む、新規なポリイミドが得られる。この脱
水、閉環、脱アルコール、閉環反応には脱水剤、脱アル
コール剤として無水酢酸、リン酸等を用いてもよい。こ
の際ジブチルスズジラウリレート、トリエチルアミン等
の有機金属系、アミン系触媒を用いることも可能であ
る。これによつて反応は進行し、かつ反応系の粘度が上
昇し、ポリイミドが生成する。Formula (I), the R 1 in (II) and (III) R 1 when the monovalent hydrocarbon group corresponding to the alcohol used when obtaining the polyamic acid ester of the above. That portion excluding the hydroxyl group from the alcohol is R 1. In order to convert this polyamic acid or polyamic acid ester to polyimide, preferably at a temperature of 100 to 300 ° C.
Heat treat for 30-50 minutes. By doing so, a novel polyimide containing the structural unit represented by the general formula [VI] can be obtained by dehydration and ring closure in the case of polyamic acid and dealcoholization and ring closure in the case of polyamic acid ester. For the dehydration, ring closure, dealcoholation, and ring closure reactions, a dehydrating agent and acetic anhydride, phosphoric acid, or the like may be used as the alcohol removing agent. In this case, it is also possible to use an organic metal-based or amine-based catalyst such as dibutyltin dilaurate or triethylamine. As a result, the reaction proceeds, the viscosity of the reaction system increases, and polyimide is produced.
(実施例) 以下、本発明を実施例により説明する。(Examples) Hereinafter, the present invention will be described with reference to examples.
参考例 ジシクロヘキシル−3,4,3′,4′−テトラカル
ボン酸およびその二無水物の合成例 (1)ジシクロヘキシル−3,4,3′,4′−テトラカルボ
ン酸テトラメチルエステルの製造電磁石による上下撹拌
装置の付いた容量500mlオートクレーブ(坂下化学機器
(株)製 SE−50型電磁上下撹拌式オートクレーブ)に
ビフエニル3,4,3′,4′−テトラカルボン酸テトラメチ
ルエステル38.6g(0.100モル)、テトラヒドロフラン19
3g及び活性炭に5重量%ロジウムを担持させた触媒(日
本エンゲルハルド社製)3.86gを仕込み、水素圧力30kg/
cm2反応温度100℃で水素化反応を行なつた。反応時間3.
5時間で水素の消費が停止し、その時の蓄圧器内の水素
圧力の減少量から求めた消費水素量は理論消費水素量
(0.60モル)の98.8%であつた。Reference Example Synthesis of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid and its dianhydride (1) Production of dicyclohexyl-3,4,3', 4'-tetracarboxylic acid tetramethyl ester Electromagnet In a 500 ml capacity autoclave equipped with a vertical stirrer (SE-50 type electromagnetic vertical stirrer type autoclave manufactured by Sakashita Chemical Instruments Co., Ltd.), 38.6 g (0.100 mol) of biphenyl 3,4,3 ', 4'-tetracarboxylic acid tetramethyl ester ), Tetrahydrofuran 19
3 g and 3.86 g of a catalyst in which 5% by weight of rhodium is supported on activated carbon (manufactured by Nippon Engelhard Co.) are charged, and a hydrogen pressure of 30 kg /
The hydrogenation reaction was performed at a reaction temperature of 100 ° C. in cm 2 . Reaction time 3.
The consumption of hydrogen stopped in 5 hours, and the amount of hydrogen consumed based on the decrease in hydrogen pressure in the accumulator at that time was 98.8% of the theoretical hydrogen consumption (0.60 mol).
反応液中の活性炭担持ロジウム触媒を濾過操作により
除去したのち、エバポレーシヨンで溶触テトラヒドロフ
ランを除去し、白色ワツクス状のジシクロヘキシル−3,
4,3′,4′−テトラカルボン酸テトラメチルエステルを3
6.87g(0.0925モル)を得た。1H−NMR(日立製作所
(株)製 日立R−250型核磁気共鳴スペクトロメータ
ー)による分析の結果、ベンゼン核水素及び炭素−炭素
二重結合に付いている水素は見出されず、水素化反応は
完結していることがわかつた。After removing the activated carbon-supported rhodium catalyst in the reaction solution by filtration, the contact tetrahydrofuran was removed by evaporation, and white wax-like dicyclohexyl-3,3 was removed.
4,3 ', 4'-tetracarboxylic acid tetramethyl ester to 3
6.87 g (0.0925 mol) were obtained. As a result of analysis by 1 H-NMR (Hitachi R-250 type nuclear magnetic resonance spectrometer manufactured by Hitachi, Ltd.), benzene nuclear hydrogen and hydrogen attached to the carbon-carbon double bond were not found, and the hydrogenation reaction was not performed. It turned out to be complete.
(2)ジシクロヘキシル−3,4,3′,4′−テトラカルボ
ン酸の製造 冷却管を取付けた1ナス形フラスコにジシクロヘキ
シル−3,4,3′4′−テトラカルボン酸テトラメチルエ
ステル29.9g(0.075モル)を入れ、これにメタノール20
0gを加え均一溶液としたのち、10%水酸化ナトリウム溶
液200gを加え、100℃の油浴に入れ、リフラツクスを6
時間行なつた。この後、エバポレーシヨンによりメタノ
ールを留去し、反応液量が140gになるまで濃縮し、これ
に36%塩酸48mlを加え、pHlとした。pH4〜5で液は白濁
し、pHlでは白色の微細な粉末が沈殿した。沈殿物を濾
過で取り出し、このあと水洗、乾燥し、17.8gの白色微
粉末結晶のジシクロヘキシル−3,4,3′,4′−テトラカ
ルボン酸を得た(0.052モル)。(2) Production of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid 29.9 g of dicyclohexyl-3,4,3'4'-tetracarboxylic acid tetramethyl ester was placed in a one-necked flask equipped with a cooling tube. 0.075 mol), and methanol 20
After adding 0 g to make a homogeneous solution, 200 g of a 10% sodium hydroxide solution was added, and the mixture was placed in an oil bath at 100 ° C., and reflux was reduced to 6 g.
Time passed. Thereafter, methanol was distilled off by evaporation, and the reaction solution was concentrated until the amount of the reaction solution reached 140 g, and 48 ml of 36% hydrochloric acid was added thereto to adjust the pH to 1. At pH 4-5, the solution became cloudy, and at pH 1 a fine white powder precipitated. The precipitate was removed by filtration, washed with water, and dried to obtain 17.8 g of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid as fine white powder crystals (0.052 mol).
この結晶の赤外吸収スペクトル(日立製作所(株)製
日立260−30型外分光光度計を用いKBr法で測定)を第
1図に示す。1H−NMRスペクトルを第2図に示す。第2
図において2.50ppmの吸収は溶媒d6−ジメチルスルホキ
シドにもとづく吸収であり、3.35ppmの吸収は溶媒に含
まれている水による吸収である。これら2つを除いた吸
収において11.95ppmのカルボキシル基プロトンにもとづ
く吸収と、0.87〜3.00ppmのシクロヘキサン環プロトン
に基づく吸収の積分強度比は、前者:後者が29:132(=
4:18.2)であり、理論値に一致した。FIG. 1 shows the infrared absorption spectrum of this crystal (measured by the KBr method using a Hitachi 260-30 external spectrophotometer manufactured by Hitachi, Ltd.). FIG. 2 shows the 1 H-NMR spectrum. Second
Absorption of 2.50ppm in figure solvent d 6 - is the absorption based on dimethyl sulfoxide, absorption of 3.35ppm is the absorption due to water contained in the solvent. In the absorption excluding these two, the integrated intensity ratio of the absorption based on the carboxyl group proton of 11.95 ppm and the absorption based on the cyclohexane ring proton of 0.87 to 3.00 ppm is 29: 132 (= former: latter).
4: 18.2), which is consistent with the theoretical value.
また、この結晶の融点は219〜222℃であり、元素分析
の結果、炭素56.24%、水素6.53%であり、計算値炭素5
6.13%、水素6.48%に一致した。The melting point of this crystal was 219 to 222 ° C. As a result of elemental analysis, it was 56.24% of carbon and 6.53% of hydrogen.
This corresponds to 6.13% and hydrogen 6.48%.
(3)ジシクロヘキシル−3,4,3′,4′−テトラカルボ
ン酸二無水物の製造 冷却管を取付けた300mlナス形フラスコにジシクロヘ
キシル−3,4,3′,4′−テトラカルボン酸15.0(0.044モ
ル)と無水酢酸180gとを仕込み、150℃の油浴に入れ、
1時間リラツクスさせた。(3) Production of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride In a 300 ml eggplant-shaped flask equipped with a cooling tube, dicyclohexyl-3,4,3', 4'-tetracarboxylic acid 15.0 ( 0.044 mol) and 180 g of acetic anhydride, and put in an oil bath at 150 ° C.
Let relax for 1 hour.
この後、熱時濾過を行ない、濾液を放冷させたとこ
ろ、白色結晶が析出した。この結晶を濾過操作で取出
し、圧力30mmHg、温度100℃で2時間乾燥した後の結晶
量は10.8g(0.035モル)であつた。Thereafter, filtration was performed while heating, and the filtrate was allowed to cool, whereby white crystals were precipitated. The crystals were taken out by filtration and dried at a pressure of 30 mmHg and a temperature of 100 ° C. for 2 hours to give 10.8 g (0.035 mol) of crystals.
結晶の融点は231〜234℃であり、元素分析の結果、炭
素62.59%、水素6.01%であり、理論値の炭素62.74%、
水素5.92%とよく一致した。The melting point of the crystal is 231 to 234 ° C. As a result of elemental analysis, it is 62.59% carbon and 6.01% hydrogen.
This was in good agreement with 5.92% of hydrogen.
この結晶の赤外吸収スペクトルを第3図に示す。1H−
NMRスペクトルを第4図に示す。第4図において、10〜1
3ppmの低磁場におけるカルボン酸プロトンの吸収はな
く、無水物になつていることがわかる。FIG. 3 shows the infrared absorption spectrum of this crystal. 1 H−
The NMR spectrum is shown in FIG. In FIG. 4, 10-1
It can be seen that there is no absorption of carboxylic acid protons in a low magnetic field of 3 ppm, and the substance is an anhydride.
実施例1 温度計、撹拌機及び塩化カルシウム管を備えた200ml
の三つ口フラスコに4,4′−ジアミノジフエニルエーテ
ル12.014g(60ミリモル)および反応溶媒としてN−メ
チル−2−ピロリドン70.92gを入れ室温で撹拌溶解させ
た。これに参考例で合成したジシクロヘキシル−3,4,
3′,4′−テトラカルボン酸二無水物18.379g(60ミリモ
ル)を加え、室温で8時間撹拌を続けた。この間、反応
時間の経過とともにポリアミド酸反応液の粘度は上昇し
てゆき、8時間撹拌を行なつた時の粘度は25℃で86ポア
ズに達した。ついで、この反応液を80℃で約5時間加熱
(クツキング)し粘度を15ポアズ調整した後、ガラス板
上に塗布して乾燥し、このポリアミド酸を一部か採取し
た。このポリアミド酸の赤外吸収スペクトル(日立製作
所(株)製 日立270−50型赤外線分光光度計を用いKBr
法で測定)を第5図に示した。次いで、ガラス板上に塗
布し乾燥したポリアミド酸を250℃で1時間熱処理して
ガラス板から剥離したところ、35μm厚さの透明性良好
なポリイミドのフイルムが得られた。このポリイミドの
フイルムの一部を採取し、上記と同様にして測定した赤
外吸収スペクトルを第6図に示した。また、このものの
Tg(ガラス転移温度)をデュポン社製 910示査走査熱
量計を用いて測定したところ244℃であつた。次にこの
ポリイミドのフイルムを以下に示す試験方法により評価
した。結果を表1に示す。Example 1 200 ml equipped with thermometer, stirrer and calcium chloride tube
Was charged with 12.014 g (60 mmol) of 4,4'-diaminodiphenyl ether and 70.92 g of N-methyl-2-pyrrolidone as a reaction solvent, and were stirred and dissolved at room temperature. Dicyclohexyl-3,4,4 synthesized in Reference Example
18.379 g (60 mmol) of 3 ', 4'-tetracarboxylic dianhydride was added and stirring was continued at room temperature for 8 hours. During this period, the viscosity of the polyamic acid reaction liquid increased with the elapse of the reaction time, and reached 86 poise at 25 ° C. with stirring for 8 hours. Then, the reaction liquid was heated (cooking) at 80 ° C. for about 5 hours to adjust the viscosity to 15 poise, applied to a glass plate and dried, and a part of the polyamic acid was collected. Infrared absorption spectrum of this polyamic acid (KBr using Hitachi 270-50 type infrared spectrophotometer manufactured by Hitachi, Ltd.)
5) is shown in FIG. Then, the polyamic acid applied and dried on the glass plate was heat-treated at 250 ° C. for 1 hour and peeled off from the glass plate to obtain a 35 μm-thick polyimide film having good transparency. A part of this polyimide film was collected, and the infrared absorption spectrum measured in the same manner as above was shown in FIG. Also,
Tg (glass transition temperature) was measured using a DuPont 910 scanning calorimeter and found to be 244 ° C. Next, this polyimide film was evaluated by the following test methods. Table 1 shows the results.
試験方法 (1)熱分解温度 上記フイルム10mgを用い、熱天秤(デュポン社製 91
0型DSC)で空気気流中昇温速度5℃/minで測定し、5%
重量減少した温度を熱分解温度とした。Test method (1) Thermal decomposition temperature Using 10 mg of the above film, heat balance (Dupont 91)
0% DSC), measured at a rate of 5 ° C / min in air stream, 5%
The temperature at which the weight was reduced was taken as the pyrolysis temperature.
(2)透過率 分光光度計(日立製作所(株)製 日立200−20型ダ
ブルビーム分光光度計)を用いて、波長700nm、600nmお
よび500nmにおける可視光透過率を測定した。(2) Transmittance The visible light transmittance at wavelengths of 700 nm, 600 nm and 500 nm was measured using a spectrophotometer (Hitachi, Ltd., Hitachi 200-20 type double beam spectrophotometer).
実施例2 4,4′−ジ(3−アミノフエノキシ)ジフエニルスル
ホン19.463g(45ミリモル)、ジシクロヘキシル−3,4,
3′4′−テトラカルボン酸二無水物13.784g(45ミリモ
ル)、N−メチル−2−ピロリドン77.58gを用いて実施
例1と同様にしてポリアミド酸溶液およびポリイミドの
フイルムを作製し、実施例1と同様の評価を行なつた結
果を表1に併せて示す。Example 2 19.463 g (45 mmol) of 4,4'-di (3-aminophenoxy) diphenylsulfone, dicyclohexyl-3,4,
A polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1 using 13.784 g (45 mmol) of 3'4'-tetracarboxylic dianhydride and 77.58 g of N-methyl-2-pyrrolidone. Table 1 also shows the results of the same evaluation as in Example 1.
比較例1 4,4′−ジアミノジフエニルエーテル8.010g(40ミリ
モル)、ピロメリツト酸二無水物8.725g(40ミリモ
ル)、N−メチル−2−ピロリドン94.83gを用いて実施
例1と同様にしてポリアミド酸溶液を得、350℃1時間
熱処理してポリイミドのフイルムを作製し、実施例1と
同様の評価を行なつた結果を表1に併せて示す。Comparative Example 1 The procedure of Example 1 was repeated except that 8.010 g (40 mmol) of 4,4'-diaminodiphenyl ether, 8.725 g (40 mmol) of pyromellitic dianhydride and 94.83 g of N-methyl-2-pyrrolidone were used. A polyamic acid solution was obtained and heat-treated at 350 ° C. for 1 hour to prepare a polyimide film. The results of the same evaluation as in Example 1 are also shown in Table 1.
比較例2 4,4′−ジアミノジフエニルエーテル15.018g(75ミリ
モル)、1,2,3,4−ブタンテトラカルボン酸二無水物14.
860g(75ミリモル)及びN−メチル−2−ピロリドン6
9.72gを用い実施例1と同様にしてポリアミド酸溶液お
よびポリイミドのフイルムを作成し、実施例1と同様の
評価を行なつた結果を表1に併せて示す。Comparative Example 2 15.018 g (75 mmol) of 4,4'-diaminodiphenyl ether, 14.2,3,4-butanetetracarboxylic dianhydride 14.
860 g (75 mmol) and N-methyl-2-pyrrolidone 6
A polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1 using 9.72 g, and the same evaluations as in Example 1 were performed. The results are also shown in Table 1.
比較例3 ジャーナルオブオーガニツクケミストリー(J.Org.Ch
em.)第31巻3438頁(1966年)で述べられている方法
で、1,2,4,5−シクロヘキサンテトラカルボン酸を合成
し、これを無水酢酸を用いて脱水閉環させ、1,2,4,5−
シクロヘキサンテトラカルボン酸二無水物を得た。この
酸無水物15.692g(70ミリモル)と4,4′−ジアミノジフ
エニルエーテル14.017g(70ミリモル)及びN−メチル
−2−ピロリドン69.321gを用い、実施例1と同様にし
てポリアミド酸の溶液を作成した。次に、実施例1と同
様にしてポリアミド酸溶液をガラス板に塗布し、乾燥後
250℃1時間の熱処理を行なつたところ、塗膜はリン片
状にぼろぼろに割れ、フイルムを形成出来なかつた。Comparative Example 3 Journal of Organic Chemistry (J.Org.Ch
em.) 1,3,4,5-cyclohexanetetracarboxylic acid was synthesized by the method described in Vol. 31, p. 3438 (1966), and this was dehydrated and ring-closed with acetic anhydride to give 1,2,4,5-cyclohexanetetracarboxylic acid. , 4,5-
Cyclohexanetetracarboxylic dianhydride was obtained. A polyamic acid solution was prepared in the same manner as in Example 1 by using 15.692 g (70 mmol) of this acid anhydride, 14.017 g (70 mmol) of 4,4'-diaminodiphenyl ether and 69.321 g of N-methyl-2-pyrrolidone. It was created. Next, a polyamic acid solution was applied to a glass plate in the same manner as in Example 1 and dried.
When heat treatment was carried out at 250 ° C. for 1 hour, the coating film cracked into scaly pieces and no film could be formed.
(発明の効果) 本発明によつて得られる新規なポリアミド酸又はポリ
アミド酸エステルは、低温でポリイミド化し新規なポリ
イミドを与える。かかるポリイミドは、透明性、耐熱性
及び機械特性が良好なものである。 (Effect of the Invention) The novel polyamic acid or polyamic acid ester obtained according to the present invention is polyimide at a low temperature to give a novel polyimide. Such a polyimide has good transparency, heat resistance and mechanical properties.
第1図は参考例(2)におけるジシクロヘキシル−3,4,
3′,4′−テトラカルボン酸の赤外吸収スペクトル、第
2図は参考例(2)におけるジシクロヘキシル−3,4,
3′,4′−テトラカルボン酸の1H−NMRスペクトル、第3
図は参考例(3)におけるジシクロヘキシル−3,4,3′,
4′−テトラカルボン酸二無水物の赤外吸収スペクト
ル、第4図は参考例(3)におけるジシクロヘキシル−
3,4,3′,4′−テトラカルボン酸二無水物の1H−NMRスペ
クトル、第5図は実施例1におけるジシクロヘキシル−
3,4,3′,4′−テトラカルボン酸二無水物と4,4′−ジア
ミノジフエニルエーテルとを反応させて得られたポリア
ミド酸の赤外吸収スペクトル、第6図は実施例1におけ
るポリアミド酸を250℃で熱処理して得られたポリイミ
ドの赤外吸収スペクトルを示す。FIG. 1 shows dicyclohexyl-3,4,4 in Reference Example (2).
Infrared absorption spectrum of 3 ', 4'-tetracarboxylic acid. FIG. 2 shows dicyclohexyl-3,4,4 in Reference Example (2).
1 H-NMR spectrum of 3 ', 4'-tetracarboxylic acid, third
The figure shows dicyclohexyl-3,4,3 ', in Reference Example (3).
Infrared absorption spectrum of 4'-tetracarboxylic dianhydride, FIG. 4 shows dicyclohexyl-
1 H-NMR spectrum of 3,4,3 ', 4'-tetracarboxylic dianhydride; FIG. 5 shows the dicyclohexyl-
Infrared absorption spectrum of polyamic acid obtained by reacting 3,4,3 ', 4'-tetracarboxylic dianhydride with 4,4'-diaminodiphenyl ether. FIG. 3 shows an infrared absorption spectrum of a polyimide obtained by heat-treating polyamic acid at 250 ° C.
Claims (1)
酸基又は水酸基とメトキシ基若しくはエトキシ基を示
す)で表わされる化合物と 一般式〔V〕 H2N−R2−NH2 〔V〕 (式中、R2は二価の基を示す)で表わされるジアミンと
を反応させることを特徴とする下記一般式〔I〕、〔I
I〕又は〔III〕で表わされる構造単位からなるポリアミ
ド酸又はポリアミド酸エステルの製造法。 (上記〔I〕、〔II〕及び〔III〕の式中、R1は水素原
子、メチル基又はエチル基、R2は2価の基を示す)1. A compound of the general formula [IV] (Wherein R 3 and R 4 each independently represent an oxygen atom, two hydroxyl groups, or a hydroxyl group and a methoxy or ethoxy group) and a compound represented by the general formula [V] H 2 N—R 2 — Reacting with a diamine represented by NH 2 [V] (wherein, R 2 represents a divalent group);
A method for producing a polyamic acid or a polyamic ester comprising the structural unit represented by I] or [III]. (In the formulas [I], [II] and [III], R 1 represents a hydrogen atom, a methyl group or an ethyl group, and R 2 represents a divalent group.)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31920687A JP2611289B2 (en) | 1987-12-17 | 1987-12-17 | Method for producing polyamic acid or polyamic acid ester |
US07/252,608 US4958001A (en) | 1987-10-08 | 1988-10-03 | Dicyclohexyl-3,4,3',4'-tetracarboxylic acid or dianhydride thereof and polyamide-acid and polyimide obtained therefrom |
DE8888309277T DE3874474T2 (en) | 1987-10-08 | 1988-10-05 | DICYCLOHEXYL-3,4,3 ', 4'-TETRACARBONIC ACID OR YOUR DIANHYDRIDE AND A POLYAMID ACID AND A POLYIMIDE PRODUCED THEREOF. |
EP88309277A EP0311374B1 (en) | 1987-10-08 | 1988-10-05 | Dicylcohexyl-3,4,3'4'-tetra-carboxylic acid or dianhydride thereof and polyamide-acid and polymide obtained therefrom |
CN95120886A CN1054616C (en) | 1987-10-08 | 1988-10-07 | Dicyclohexyl-3,4,3',4'-tetracarboxylic acid or dianhydride thereof and polyamide-acid and polyimide obtained therefrom |
KR1019880013180A KR910005229B1 (en) | 1987-10-08 | 1988-10-08 | Dicyolhexyl-3,4,3',4'-tetracarboxylic acid or pianhydride obtained therefrom |
CN88108953A CN1040263C (en) | 1987-12-17 | 1988-12-24 | Cathode of electron tube |
KR1019910008003A KR920002232B1 (en) | 1987-10-08 | 1991-05-16 | Orientation film used in a liquid crystal display device |
KR1019910008002A KR920004807B1 (en) | 1987-10-08 | 1991-05-16 | Polyamide acide or polyamide ester and polyimide and its method of producing |
CN93117739A CN1033858C (en) | 1987-10-08 | 1993-09-15 | Dicyclohexyl-3,4,3',4'-tetracarboxylic acid or dianhydride thereof and polyamide-acid and polyimide obtained therefrom |
CN99124375A CN1258015A (en) | 1987-10-08 | 1999-11-26 | Oriented film prepared from polyimide and liquid crystal display contg. same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31920687A JP2611289B2 (en) | 1987-12-17 | 1987-12-17 | Method for producing polyamic acid or polyamic acid ester |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25960295A Division JP2616497B2 (en) | 1995-10-06 | 1995-10-06 | Polyimide manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01161021A JPH01161021A (en) | 1989-06-23 |
JP2611289B2 true JP2611289B2 (en) | 1997-05-21 |
Family
ID=18107593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31920687A Expired - Lifetime JP2611289B2 (en) | 1987-10-08 | 1987-12-17 | Method for producing polyamic acid or polyamic acid ester |
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JP4543575B2 (en) * | 2001-04-25 | 2010-09-15 | 宇部興産株式会社 | rac-trans-dicyclohexyl-3,3 ', 4,4'-tetracarboxylic acid, dianhydrides and process for their preparation |
JP4543576B2 (en) * | 2001-04-25 | 2010-09-15 | 宇部興産株式会社 | rac-cis-dicyclohexyl-3,3 ', 4,4'-tetracarboxylic acid, dianhydrides and process for their preparation |
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